Polyurethanes derived from non-fluorinated or partially fluorinated polymers

ABSTRACT

Polymers are described having repeat units of Formula (I): 
                         
wherein R 3  is H or alkyl group; x and t are positive integers; Q is C(O)O, C(O)NH, or direct bond; D is alkylene, arylene, or (CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m ; E is O, S, NR 5 , or direct bond; R 5  is H or alkyl; G is the residue of a polyisocyanate; V is a urethane, urea, or thiourea that bonds to other parts of the polymer compound or to a monovalent blocking group; s is 1 to 5; Y is O or a substituted or unsubstituted arylene group; A is an alkylene group; w, v, and y are 0 or 1; X is the residue of a cyclic or acyclic sugar alcohol which is substituted with —R 1 , —C(O)R 1 , —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 , —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 , or mixtures thereof; n and m are independently 0 to 20; R 1  is independently an alkyl group; and R 2  is independently —H or alkyl group.

FIELD OF INVENTION

This invention relates to urethane, urea, or thiourea compounds ofisocyanate-reactive oligomers or polymers, the isocyanate-reactiveoligomers or polymers being derived from substituted sugar alcohols.

BACKGROUND OF THE INVENTION

Various compositions are known to be useful as treating agents toprovide water repellency and optionally stain release to textilesubstrates. Many such treating agents are fluorinated polymers andcopolymers, or non-fluorinated polymers and copolymers. Non-fluorinatedcompounds are predominately polyacrylate-based or urethane-basedcopolymers.

Fluorinated copolymers provide good repellency to water and oil. Variousattempts have been made to produce a non-fluorinated water repellent.Some non-fluorinated copolymers are known to provide water repellencyand optionally stain release to textiles, but are less effective thanthe fluorinated counterparts.

Elsbernd et al., in U.S. Pat. No. 7,750,093, disclose a polyurethanepolymer derived from oligomeric fluoroacrylates that provides oil andwater repellency to textile substrates.

SUMMARY OF INVENTION

The need exists for non-fluorinated or partially fluorinatedcompositions that provide water repellency and optionally stain releasefor textiles, with performance results comparable to fluorinatedtreating agents. Also desirable is a non-fluorinated or partiallyfluorinated composition that can be bio-based derived. The presentinvention meets these needs.

In one embodiment, the present invention is a polymer compoundcomprising the repeat units of Formula (I):

wherein R³ is selected from H or a C₁ to C₄ alkyl group; x and t areintegers from 1 to 200; Q is C(O)O, C(O)NH, or a direct bond; D is a C₁to C₆ linear or branched alkylene, an arylene group, or(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m), E is O, S, NR⁵, or a direct bond;provided that E is a direct bond when D is(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m); R⁵ is H or a monovalent C₁ to C₆ alkyl;G is the residue of a diisocyanate or polyisocyanate; V is a groupselected from urethane, urea, or thiourea that bonds to other parts ofthe polymer compound or to a monovalent blocking group; s is 1 to 5; Yis selected from O, a substituted arylene group, or an unsubstitutedarylene group; A is a linear or branched C₁ to C₁₀ alkylene group; w is0 or 1; v is 0 or 1; y is 0 or 1; provided that w+y is at least 1; if wis 0 then Y is a substituted or unsubstituted arylene group; and if Y isO then v is 1; X is the residue of a cyclic or acyclic sugar alcoholwhich is substituted with at least one —R¹, —C(O)R¹,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹, or mixtures thereof; where thecyclic or acyclic sugar alcohol is selected from a saccharide, reducedsugar, aminosaccharide, aldonic acid, or aldonic acid lactone; whereineach n is independently 0 to 20; each m is independently 0 to 20; m+n isgreater than 0; each R¹ is independently a linear or branched alkylgroup having 5 to 29 carbons optionally comprising at least 1unsaturated bond; and each R² is independently —H, a linear or branchedalkyl group having 6 to 30 carbons optionally comprising at least 1unsaturated bond, or mixtures thereof.

In another embodiment, the invention relates to a method of preparing apolymer compound comprising (i) reacting (a) at least one compoundselected from Formula (IV)

with (b) at least one compound selected from Formula (V)

(ii) optionally reacting at least one additional ethylenicallyunsaturated monomer; (iii) subsequently reacting the product of step (i)or (ii) with at least one diisocyanate or polyisocyanate; and (iv)optionally reacting at least one additional isocyanate-reactive compoundduring step (iii) or following step (iii); wherein R³ is selected from Hor a C₁ to C₄ alkyl group; Q is C(O)O, C(O)NH, or a direct bond; D is aC₁ to C₆ linear or branched alkylene, an arylene group, or(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m); J is H, OH, N(R⁵)₂, C(O)OH, or SH;provided that J is H only when D is (CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m); R⁵is H or a C₁ to C₆ alkyl; Y is selected from O, a substituted arylenegroup, or an unsubstituted arylene group; A is a linear or branched C₁to C₁₀ alkylene group; w is 0 or 1; v is 0 or 1; y is 0 or 1; providedthat w+y is at least 1; if w is 0 then Y is a substituted orunsubstituted arylene group; and if Y is O then v is 1; X is the residueof a cyclic or acyclic sugar alcohol which is substituted with at leastone —R¹, —C(O)R′, —(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹, or mixtures thereof; where thecyclic or acyclic sugar alcohol is selected from a saccharide, reducedsugar, aminosaccharide, aldonic acid, or aldonic acid lactone; whereineach n is independently 0 to 20; each m is independently 0 to 20; m+n isgreater than 0; each R¹ is independently a linear or branched alkylgroup having 5 to 29 carbons optionally comprising at least 1unsaturated bond; and each R² is independently —H, a linear or branchedalkyl group having 6 to 30 carbons optionally comprising at least 1unsaturated bond, or mixtures thereof.

DETAILED DESCRIPTION OF INVENTION

Herein all trademarks are designated with capital letters.

The present invention comprises urethanes, ureas, and thioureas madefrom aqueous non-fluorinated or partially fluorinated organic polymercompositions useful for imparting durable water repellency andoptionally stain release to textiles. The organic polymer compositionsare derived from substituted sugar alcohols. The compounds of thisinvention provide increased durable water repellency and optionallystain release to textiles and are comparable to several fluorinatedwater repellent compounds.

In one embodiment, the present invention is a polymer compoundcomprising the repeat units of Formula (I):

wherein R³ is selected from H or a C₁ to C₄ alkyl group; x and t areintegers from 1 to 200; Q is C(O)O, C(O)NH, or a direct bond; D is a C₁to C₆ linear or branched alkylene, an arylene group, or(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m), E is O, S, NR⁵, or a direct bond;provided that E is a direct bond when D is(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m); R⁵ is H or a monovalent C₁ to C₆ alkyl;G is the residue of a diisocyanate or polyisocyanate; V is a groupselected from urethane, urea, or thiourea that bonds to other parts ofthe polymer compound or to a monovalent blocking group; s is 1 to 5; Yis selected from O, a substituted arylene group, or an unsubstitutedarylene group; A is a linear or branched C₁ to C₁₀ alkylene group; w is0 or 1; v is 0 or 1; y is 0 or 1; provided that w+y is at least 1; if wis 0 then Y is a substituted or unsubstituted arylene group; and if Y isO then v is 1; X is the residue of a cyclic or acyclic sugar alcoholwhich is substituted with at least one —R¹, —C(O)R¹,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹, or mixtures thereof; where thecyclic or acyclic sugar alcohol is selected from a saccharide, reducedsugar, aminosaccharide, aldonic acid, or aldonic acid lactone; whereineach n is independently 0 to 20; each m is independently 0 to 20; m+n isgreater than 0; each R¹ is independently a linear or branched alkylgroup having 5 to 29 carbons optionally comprising at least 1unsaturated bond; and each R² is independently —H, a linear or branchedalkyl group having 6 to 30 carbons optionally comprising at least 1unsaturated bond, or mixtures thereof. The repeat units of the polymermay be situated in any order to form random copolymers, blockcopolymers, or other configurations, and the polymer compounds may alsoinclude additional repeat units in any order.

The term “residue of a cyclic or acyclic sugar alcohol” is hereindefined as the molecular structure of a cyclic or acyclic sugar alcoholwhen one or more H atoms has been removed from a hydroxyl group —OH. InFormula (I), the bond of X to C═O forms an ester functional group (y=0)or urethane functional group (y=1). The term “residue of a diisocyanateor polyisocyanate” is herein defined as the molecular structure of adiisocyanate or polyisocyanate when all —NCO groups have been removed.In Formula (I), the —NCO groups from the diisocyanate or polyisocyanateform urethane, urea, or thiourea linkages to the polymer backbone, formurethane, urea, or thiourea crosslinks, or bond to an optional blockinggroup.

In another embodiment, the invention relates to a method of preparing apolymer compound comprising (i) reacting (a) at least one compoundselected from Formula (IV)

with (b) at least one compound selected from Formula (V)

(ii) optionally reacting at least one additional ethylenicallyunsaturated monomer; (iii) subsequently reacting the product of step (i)or (ii) with at least one diisocyanate or polyisocyanate; and (iv)optionally reacting at least one additional isocyanate-reactive compoundduring step (iii) or following step (iii); wherein R³ is selected from Hor a C₁ to C₄ alkyl group; Q is C(O)O, C(O)NH, or a direct bond; D is aC₁ to C₆ linear or branched alkylene, an arylene group, or(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m); J is H, OH, N(R⁵)₂, C(O)OH, or SH;provided that J is H only when D is (CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m); R⁵is H or a C₁ to C₆ alkyl; Y is selected from 0, a substituted arylenegroup, or an unsubstituted arylene group; A is a linear or branched C₁to C₁₀ alkylene group; w is 0 or 1; v is 0 or 1; y is 0 or 1; providedthat w+y is at least 1; if w is 0 then Y is a substituted orunsubstituted arylene group; and if Y is O then v is 1; X is the residueof a cyclic or acyclic sugar alcohol which is substituted with at leastone —R¹, —C(O)R¹, —(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹, or mixtures thereof; where thecyclic or acyclic sugar alcohol is selected from a saccharide, reducedsugar, aminosaccharide, aldonic acid, or aldonic acid lactone; whereineach n is independently 0 to 20; each m is independently 0 to 20; m+n isgreater than 0; each R¹ is independently a linear or branched alkylgroup having 5 to 29 carbons optionally comprising at least 1unsaturated bond; and each R² is independently —H, a linear or branchedalkyl group having 6 to 30 carbons optionally comprising at least 1unsaturated bond, or mixtures thereof.

The compound of Formula (IV) may be formed by any suitable method,including by reacting an ethylenically unsaturated monomer having acarboxylic acid, acyl halide, amide, isocyanate, diisocyanate,polyisocyanate functional group with a cyclic or acyclic sugar alcoholwhich is substituted with at least one —R¹; —C(O)R¹;—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²; —(CH₂CH₂O)_(n)(CH(CH₃)CHO)_(m)C(O)R¹;or mixtures thereof. For example, the compound of Formula (IV) may bemade by reacting (c) a compound selected from Formula (VI)

with (d) at least one cyclic or acyclic sugar alcohol which issubstituted with at least one —R¹, —C(O)R¹,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹, or mixtures thereof; where Y, A,R³, w, v, y, R¹, R², m, and n are defined as above; Z is selected from ahalide, —OC(O)CR³═CH₂, —OH, or —NH₂ when y is 0 and Z is —NCO when y is1.

The cyclic or acyclic sugar alcohol is selected from a saccharide,reduced sugar, aminosaccharide, aldonic acid, or aldonic acid lactone,and is substituted with at least one —R¹; —C(O)R¹;—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²;—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹; or mixtures thereof. Such asubstitution lends hydrophobic character to the polymer. In oneembodiment, the cyclic or acyclic sugar alcohol is substituted with atleast two —R¹; —C(O)R¹; —(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²;—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹; or mixtures thereof; and inanother embodiment, it is substituted with at least three —R¹; —C(O)R¹;—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²;—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹; or mixtures thereof. Examples ofsuch sugar alcohols include but are not limited to aldoses and ketosessuch as those compounds derived from tetroses, pentoses, hexoses, andheptoses. Specific examples include glucose, glyceraldehyde, erythrose,arabinose, ribose, arabinose, allose, altrose, mannose, xylose, lyxose,gulose, glactose, talose, fructose, ribulose, mannoheptulose,sedohelptulose, threose, erythritol, threitol, glucopyranose,mannopyranose, talopyranose, allopyranose, altropyranose, idopyranose,gulopyranose, glucitol, mannitol, erythritol, sorbitol, arabitol,xylitol, ribitol, galactitol, fucitol, iditol, inositol,pentaerythritol, dipentaerythritol, volemitol, gluconic acid, glycericacid, xylonic acid, galactaric acid, ascorbic acid, citric acid,gluconic acid lactone, glyceric acid lactone, xylonic acid lactone,glucosamine, galactosamine, or mixtures thereof.

The cyclic or acyclic sugar alcohols are substituted with at least one—R¹; —C(O)R¹; —(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²; or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹ by any suitable method, includingesterification with a fatty acid, to form hydroxy-functional substitutedsugar alcohols. In one embodiment, the fatty acid substitution of thecyclic or acyclic sugar alcohols has a melting point of at least −59° C.In another embodiment, the fatty acid substitution of the cyclic oracyclic sugar alcohols has a melting point of at least 0° C., and in athird embodiment, the fatty acid substitution of the cyclic or acyclicsugar alcohols has a melting point of at least 40° C. Suitable fattyacids include, but are not limited to, caprylic acid, capric acid,lauric acid, mysteric acid, palmitic acid, stearic acid, arachidic acid,behenic acid, lignoceric acid, palmitoleic acid, lineolic acid, oleicacid, erucic acid, and mixtures thereof. In one embodiment, R¹ is alinear or branched alkyl group having 7 to 29 carbons, in anotherembodiment, R¹ is a linear or branched alkyl group having 9 to 29carbons, and in another embodiment, R¹ is a linear or branched alkylgroup having 11 to 21 carbons. In one embodiment, R² is a linear orbranched alkyl group having 8 to 30 carbons, in another embodiment, R²is a linear or branched alkyl group having 10 to 30 carbons, and inanother embodiment, R² is a linear or branched alkyl group having 12 to22 carbons.

In one embodiment, X is selected from Formulas (IIa), (IIb), or (IIc):

wherein each R is independently a direct bond to C═O of Formula I, —H,—R¹, —C(O)R¹, —(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R², or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹; n and m are defined as above; m+nis greater than 0; r is 1 to 3; a is 0 or 1; p is independently chosenfrom 0 to 2; provided that a is 0 when r is 3; each R¹ and R² aredefined as above; provided when X is Formula (IIa), then one R is adirect bond to C═O of Formula 1; and at least one R is a —R¹, —C(O)R¹,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R², or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹; each R⁴ is independently a directbond to C═O of Formula I, —H, a linear or branched alkyl group having 6to 30 carbons optionally comprising at least 1 unsaturated bond orcombinations thereof, —(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R², or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹; provided when X is Formula (IIb),then one R or R⁴ is a direct bond to C═O of Formula 1; and at least oneR or R⁴ is a linear or branched alkyl optionally comprising at least 1unsaturated bond or combinations thereof,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R², or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹; and each R¹⁹ is a direct bond toC═O of Formula I, —H, —C(O)R¹, or —CH₂C[CH₂OR]₃, provided when X isFormula (IIc), then one R¹⁹ or R is a direct bond to C═O of Formula I;and at least one R¹⁹ or R is —C(O)R¹, —(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²,or —(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹. In Formulas (IIa), (IIb), or(IIc), the —(CH₂CH₂O)— represents oxyethylene groups (EO) and—(CH(CH₃)CH₂O)— represents oxypropylene groups (PO). These compounds cancontain only EO groups, only PO groups, or mixtures thereof. Thesecompounds can also be present as a tri-block copolymer designatedPEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethyleneglycol), for example.

Where X is Formula (IIa), any suitable substituted reduced sugar alcoholmay (d) be employed, including esters of 1,4-sorbitan, esters of2,5-sorbitan, and esters of 3,6-sorbitan. In one embodiment, X isselected from Formula (IIa) to be Formula (IIa′):

wherein R is further limited to independently a direct bond to C═O, —H,—R¹, or —C(O)R¹. In one embodiment, at least one R is —C(O)R¹ or R¹.Compounds (d) used to form residues X of Formula (Hal having at leastone of R as —H and at least one R selected from —C(O)R¹, are commonlyknown as alkyl sorbitans. These sorbitans can be mono-substituted,di-substituted, or tri-substituted with —C(O)R¹. It is known thatcommercially available sorbitans, such as SPAN, contain a mixture of thevarious sorbitans ranging from where each R is H (un-substituted), andsorbitans where each R is —C(O)R¹ (fully substituted); wherein R¹ is alinear or branched alkyl group having 5 to 29 carbons; and mixtures ofvarious substitutions thereof. The commercially available sorbitans mayalso include amounts of sorbitol, isosorbide, or other intermediates orbyproducts.

In one embodiment, at least one R is —C(O)R¹, and R¹ is a linearbranched alkyl group having 5 to 29 carbons. Preferred compounds (d)used to form these residues include mono-, di-, and tri-substitutedsorbitans derived from caprylic acid, capric acid, lauric acid, mystericacid, palmitic acid, stearic acid, arachidic acid, behenic acid,lignoceric acid, and mixtures thereof. Particularly preferred compoundsused to form X include mono-, di-, and tri-substituted sorbitanstearates or sorbitan behenins.

Optionally, R¹ is a linear or branched alkyl group having 5 to 29carbons comprising at least 1 unsaturated bond. Examples of compounds(d) used to form residues X of Formula (IIa′) wherein at least one R isselected from —C(O)R¹, and R¹ contains least 1 unsaturated bond,include, but are not limited to, sorbitan trioleate (i.e., wherein R¹ is—C₇H₁₄CH═CHC₈H₁₇). Other examples include but are not limited to mono-,di-, and tri-substituted sorbitans derived from palmitoleic acid,lineolic acid, arachidonic acid, and erucic acid.

In one embodiment, X of Formula (IIa′) is employed, wherein R is furtherlimited to independently a direct bond to C═O, —H,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R², or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹. In this embodiment, at least oneR is independently —(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R² or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹. Compounds (b) forming X ofFormula (IIa′), wherein at least one R is—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R² or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹, wherein each m is independently 0to 20, each n is independently 0 to 20, and n+m is greater than 0 areknown as polysorbates and are commercially available under the tradenameTWEEN. These polysorbates can be mono-substituted, di-substituted, ortri-substituted with alkyl groups R¹ or R². It is known thatcommercially available polysorbates, contain a mixture of the variouspolysorbates ranging from where each R² is H (unsubsituted), andpolysorbates where each R¹ is a linear or branched alkyl group having 5to 29 carbons (fully substituted); and mixtures of various substitutionsthereof. Examples of compounds used to form X of Formula (IIa′) includepolysorbates such as polysorbate tristearate, and polysorbatemonostearate. Examples of compounds (b) used to form X of Formula (IIa′)wherein m+n is greater than 0, and wherein R¹ comprises at least 1unsaturated bond, include but are not limited to, polysorbate trioleate(wherein R¹ is C₇H₁₄CH═CHC₈H₁₇), are sold commercially under the namePolysorbate 80. Reagents may include mixtures of compounds havingvarious values for R, R¹, and R², and may also include mixtures ofcompounds where R¹ comprises at least one unsaturated bond withcompounds where R¹ is fully saturated. In one aspect, R² is H and m is apositive integer.

In one embodiment, X is selected from Formula (IIb). Compounds (d) usedto form X of Formula (IIb) are known as alkyl citrates. These citratescan be present as a mono-substituted, di-substituted, or tri-substitutedcompound with alkyl groups. It is known that commercially availablecitrates contain a mixture of the various citrates as well as citricacids from where R and each R⁴ is —H, ranging to citrates where each R⁴is a linear or branched alkyl group having 6 to 30 carbons optionallycomprising at least 1 unsaturated bond; and mixtures of varioussubstitutions thereof. Mixtures of citrates having various values forR¹, R², and R⁴ may be used, and may also include mixtures of compoundswhere R¹ comprises at least one unsaturated bond with compounds where R¹is fully saturated. Alkyl citrates are also commercially availablewherein m+n is greater than 0, R⁴ is —(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²;or —(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹ and are present in the varioussubstitutions from wherein R and each R² is H to wherein each R¹ and/orR² is a linear or branched alkyl group having 5 to 30 carbons optionallycomprising at least 1 unsaturated bond. Examples of compounds used toform X of Formula (IIb) include, but are not limited to, trialkylcitrates.

In one embodiment, X is selected from Formula (IIc). Compounds (d) usedto form X of Formula (IIc) are known as pentaerythriol esters. Thesepentaerythriol esters can be present as a mono-substituted,di-substituted, or tri-substituted with alkyl groups. Preferredcompounds used to form X of Formula (IIc) are dipentaerythriol esters,where R¹⁹ is —CH₂C[CH₂OR]₃. It is known that commercially availablepentaerythriol esters contain a mixture of the various pentaerythriolesters where R¹⁹ and each R is —H, ranging to pentaerythriol esterswhere each R is —C(O)R¹, and R¹ is a linear or branched alkyl grouphaving 5 to 29 carbons optionally comprising at least 1 unsaturatedbond; and mixtures of various substitutions thereof. The pentaerythriolesters also may contain compounds with mixtures of different chainlengths for R, or mixtures of compounds where R¹ comprises at least oneunsaturated bond with compounds where R¹ is fully saturated.

Compound (d) and residue X of Formulas (IIa), (IIb), and (IIc) can allbe bio-based derived. By “bio-based derived”, it is meant that at least10% of the material can be produced from non-crude oil sources, such asplants, other vegetation, and tallow. In one embodiment, X is from about10% to 100% bio-based derived. In one embodiment, X is from about 35% to100% bio-based derived. In another embodiment, X is from about 50% to100% bio-based derived. In one embodiment, X is from about 75% to 100%bio-based derived. In one embodiment, X is 100% bio-based derived. Theaverage OH value of the substituted sugar alcohol compounds used to formX can range from just greater than 0 to about 230. In one embodiment,the average OH value is from about 10 to about 175, and in anotherembodiment, the average OH value is from about 25 to about 140.

In one embodiment, Formula (IV) is chosen such that w is 1 and y is 0.Such a compound can be formed by reacting compound (d) at least onecyclic or acyclic sugar alcohol which is substituted with at least oneR¹, —C(O)R¹, —(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R², or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹ with a compound (c) of Formula(VI), where w is 1, y is 0, and Z is selected from a halide,—OC(O)CR²⁰═CH₂, —OH, or —NH₂. For example, the alcohol compound (d) maybe combined with triethylamine in solvent, followed by a gradualaddition of acryloyl chloride or methacryloyl chloride. The solid isremoved, typically by filtration, and washed with organic solvent, andthen purified, usually by extraction and water-washing, concentratingand drying under vacuum. In another method, compounds of the inventioncan be prepared from the substituted sugar alcohols (d) by reacting withacrylamide or with acrylic, methacrylic or chloroacrylic acid in thepresence of an acid catalyst, such as toluenesulfonic acid, and asolvent, such as hexane, cyclohexane, heptane, octane, or toluene. Theorganic layer is washed with water, isolated, and then purified,typically by vacuum distillation. Optionally, inhibitors such as4-methoxyphenol may be added during or after synthesis.

In another embodiment, Formula (IV) is chosen such that w is 1, y is 1,and Y is O. Such a compound can be formed by reacting compound (d) witha compound (c) of Formula (VI), where w is 1, y is 1, Y is O, and Z is—NCO. Any isocyanate compound fitting this formula may be used, and theinventive compound may be synthesized using conventional urethanesynthesis techniques. In one further embodiment, Formula (IV) is chosensuch that w is 0, y is 1, and Y is a substituted or unsubstitutedarylene group. Such a compound may be formed by reacting compound (d)with a compound (c) of Formula (VI), where w is 0, y is 1, Y is asubstituted or unsubstituted arylene group, and Z is —NCO. Anyisocyanate compound fitting this formula may be used, including but notlimited to substituted or unsubstituted styrene isocyanates. Theinventive compounds may be synthesized using conventional urethanesynthesis techniques. For example, the isocyanate compound (c) may becombined with the substituted sugar alcohol compound (d) and a catalystin organic solvent, heating with stirring until the solution testsnegative for active isocyanate groups, and collected.

In one embodiment, the invention relates to a mixture of compounds ofFormula (IV). In addition to compounds of the present invention asdescribed herein, these compositions may also comprise additionalcompounds that are present from commercially available sorbitans,polysorbates, alkyl citrates, or pentaethritols. These compounds can bepresent as a mixture of the various substituted sugar alcohols fromfully unsubstituted to fully substituted, and the various substitutionsin between, and optionally, the linear or branched alkyl group having 5to 29 carbons comprises at least 1 unsaturated bond.

Compound (b) having Formula (V) may be any suitable ethylenicallyunsaturated monomer having an isocyanate-reactive functional group.Examples of such monomers include but are not limited tohydroxyl-functional monomers such as N-methylol acrylamide, hydroxyethyl(meth)acrylate or (meth)acrylamide, hydroxypropyl (meth)acrylate or(meth)acrylamide, hydroxybutyl (meth)acrylate or (meth)acrylamide,hydroxyhexyl (meth)acrylate or (meth)acrylamide, hydroxydecyl(meth)acrylate or (meth)acrylamide, hydroxydodecyl (meth)acrylate or(meth)acrylatemide, or ethoxylated or propoxylated (meth)acrylates or(meth)acrylamides; amine-functional monomers such as2-(diethylamino)ethyl (meth)acrylate; and carboxylic acid-functionalmonomers such as acrylic acid and methacrylic acid.

One or more additional ethylenically unsaturated comonomers may bereacted with monomers of Formulas (IV) and (V), such as those having afunctional group selected from linear or branched hydrocarbon, linear orbranched fluorocarbon, ether, anhydride, oxyalkylene, ester, formate,carbamate, urea, amide, sulfonate, sulfonic acid, sulfonamide, halide,saturated or unsaturated cyclic hydrocarbon, morpholine, pyrrolidine,piperidine, or mixtures thereof. The additional ethylenicallyunsaturated monomer can be any monomer having an ethylenicallyunsaturated bond including, but not limited to, allyl esters such asallyl acetate, alkyl vinyl ethers, unsaturated acid esters such aslinear or branched alkyl (meth)acrylates, linear or branched fluoroalkyl(meth)acrylates optionally interrupted by O, CH₂, CH₂CH₂, or SO₂NH,unsaturated nitriles such as acrylonitrile or methacrylonitrile,alkoxylated (meth)acrylates, (meth)acylic acid, vinyl or vinylidenechloride, glycidyl (meth)acrylate, vinyl acetate, urethane or urea(meth)acrylates, (meth)acrylamides, styrene, alpha-methylstyrene,chloromethyl-substituted styrene, ethylenediol di(meth)acrylate,2-acrylamido-2-methyl-1-propane sulfonic acid (AMPS), and maleicanhydride. Suitable monomers include those listed above but also includeother ethylenically unsaturated monomers that have been shown useful inhydrophobic polymers for fibrous substrates.

Specific fluorinated ethylenically unsaturated monomers used toincorporate fluoroalkyl functionality include but are not limited toR_(f)CH₂CH₂OC(O)CR³═CH₂, R_(f)SO₂NHCH₂CH₂OC(O)CR³═CH₂,R_(f)CH₂CH₂SCH₂CH₂OC(O)CR³═CH₂, R_(f)CH₂CH₂CF₂CF₂CH₂CH₂OC(O)CR³═CH₂,R_(f)CH₂CH₂(CF₂CF₂CH₂CH₂)₂OC(O)CR³═CH₂, R_(f)CH₂CF₂CH₂CH₂OC(O)CR³═CH₂,R_(f)CH₂CF₂CH₂CF₂CH₂CH₂OC(O)CR³═CH₂, R_(f)OCF₂CF₂CH₂CH₂OC(O)CR³═CH₂,R_(f)CH₂OCH₂CH₂OC(O)CR³═CH₂, R_(f)CHFCH₂CH₂OH,R_(f)CH₂O(CH₂)₆OC(O)CR³═CH₂, (CF₃)₂CFCH₂CH₂OC(O)CR³═CH₂,(CF₃)₂CFCH₂CH₂CH₂OC(O)CR³═CH₂, R_(f)CH₂CH₂SO₂NHCH₂CH₂OC(O)CR³═CH₂,R_(f)CH₂CH₂SO₂N(CH₃)CH₂CH₂OC(O)CR³═CH₂,R_(f)CH₂CH₂SO₂N(CH₂CH₃)CH₂CH₂OC(O)CR³═CH₂,R—(CF(CF₃)CF₂O)_(y)CH₂OC(O)CR³═CH₂,CF₂═CFOCF₂CF(CF₃)OCF₂CF₂CH₂OC(O)CR³═CH₂, orR_(f)CH₂OC₂F₄CH₂OCH₂CH₂OC(O)CR³═CH₂, where R_(f) is a linear or branchedfluoroalkyl of C₁-C₂₀, or CH₂═CH—COO—C₂H₄—N(CH₃)—SO₂—C₂H₄—C₆F₁₃,2-[methyl[(3,3,4,4,5,5,6,6,6-nonfluorohexyl)sulfonyl]amino]ethylacrylate,2-[methyl[(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)sulfonyl]amino]ethylmethacrylate, or2-[[(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)sulfonyl]amino]ethylmethacrylate. In one embodiment, R_(f) is a C₂ to C₆ perfluoroalkyl.

The isocyanate-reactive polymers can be synthesized by any means knownto one skilled in the art. For example, the monomer or monomers may becontacted in a solvent system, such as isopropyl alcohol and/or methylisobutyl ketone, with a polymerization initiator, the mixture is heatedto the activation temperature of the initiator, and the polymerizationis allowed to propagate. The polymer mixture can then be contacted withan aqueous, and the organic solvents are removed, such as bydistillation. The final product is an aqueous dispersion or emulsion.

When a comonomer is selected from Formula (Vila) or Formula (VIIb),CH₂═C(R⁹)C(O)Q(CH₂)_(q)(CHR⁹)_(i)NR¹⁰R¹¹  (VIIa)CH₂═C(R⁹)NR¹²R¹³  (VIIb)or a mixture thereof, is used, wherein R⁹ is independently selected fromH or CH₃; R¹⁰ and R¹¹ are each independently C₁ to C₄ alkyl,hydroxyethyl, or benzyl; or R¹⁰ and R¹¹ together with the nitrogen atomform a morpholine, pyrrolidine, or piperidine ring; R¹² and R¹³ are eachindependently selected from H or C₁ to C₄ alkyl; Q is —O— or —NR¹⁴—wherein R¹⁴ is H or C₁-C₄ alkyl; i is 0 to 4, and q is 1 to 4, then thenitrogen bonded to R¹⁰ and R¹¹ may be from about 0% to 100% salinized,quaternized, or present as an amine oxide. The copolymers of thisembodiment can be synthesized by any means known to one skilled in theart. The copolymer may be optionally partially or completely salinizedor quarternized by conventional techniques known to those skilled in theart. In one aspect, the degree of salinization or quarternization isfrom about 50% to about 100%. Preferably, the copolymers are synthesizedby combining the monomers in a solvent system, such as isopropyl alcoholand methyl isobutyl ketone, heating the mixture to the activationtemperature of an initiator, slowly introducing an initiator into themonomer mixture, and allowing the copolymerization to propagate. Thepolymer mixture can then be contacted with an aqueous salinizationsolution, such as acetic acid solution, and the organic solvents areremoved, preferably by distillation. The final product is an aqueousemulsion.

The isocyanate-reactive polymer compounds may be in form of an aqueousdispersion or aqueous emulsion, and may further comprise a solventselected from organic solvents. The polymer compounds may be in the formof homopolymers or copolymers, and may be completely non-fluorinated ormay be partially fluorinated by the copolymerization with one or morefluorinated monomers. They may have a number average molecular weight of5000 to 200,000. In one embodiment, the polymers have a number averagemolecular weight of 50,000 to 200,000.

It will be apparent to one skilled in the art that many changes to anyor all of the above procedures can also be used to optimize the reactionconditions for obtaining maximum yield, productivity, or productquality.

To form the urethane, urea, or thiourea-functional repeat units ofFormula (I), an ethylenically unsaturated isocyanate-reactive polymercan then be reacted with at least one diisocyanate or polyisocyanate. Inone embodiment, residue G is a divalent or polyvalent moiety selectedfrom linear or branched, cyclic or acyclic, alkylene groups optionallycontaining at least one group selected from alkoxy, phenyl, siloxane,urethane, urea, biuret, uretdione, cyclized isocyanate, allophanate, orisocyanurate. The diidocyanate or polyisocyanate adds to the branchednature of the polymer by forming bonds at multiple points with thepolymer backbone, or by linking the polymer backbone with a blockinggroup. The term “polyisocyanate” is defined as tri- andhigher-functional isocyanates, and the term includes oligomers. Anydiisocyanate or polyisocyanate having predominately two or moreisocyanate groups, or any isocyanate precursor of a polyisocyanatehaving predominately two or more isocyanate groups, is suitable for usein this invention. For example, hexamethylene diisocyanate homopolymersare suitable for use herein and are commercially available. In thiscase, G would be a linear C₆ alkylene having cyclized isocyanate groups.It is recognized that minor amounts of diisocyanates can remain inproducts having multiple isocyanate groups. An example of this is abiuret containing residual small amounts of hexamethylene diisocyanate.

Also suitable for use as the polyisocyanate reactant are hydrocarbondiisocyanate-derived isocyanurate trimers, where G is a trivalent linearalkylene having an isocyanurate group. Preferred is DESMODUR N-100 (ahexamethylene diisocyanate-based compound available from BayerCorporation, Pittsburgh, Pa.). Other triisocyanates useful for thepurposes of this invention are those obtained by reacting three moles oftoluene diisocyanate, where G is a trivalent polyaromatic ring structurehaving a cyclized isocyanate group. The isocyanurate trimer of toluenediisocyanate and that of 3-isocyanatomethyl-3,4,4-trimethylcyclohexylisocyanate are other examples of triisocyanates useful for the purposesof this invention, as is methane-tris-(phenylisocyanate). Precursors ofpolyisocyanate, such as diisocyanate, are also suitable for use in thepresent invention as substrates for the polyisocyanates. DESMODURN-3300, DESMODUR N-3600, DESMODUR Z-4470, DESMODUR H, DESMODUR N3790,and DESMODUR XP 2410, from Bayer Corporation, Pittsburgh, Pa., andbis-(4-isocyanatocylohexyl)methane are also suitable in the invention.

Preferred polyisocyanate reactants are the aliphatic and aromaticpolyisocyanates containing biuret structures, or polydimethyl siloxanecontaining isocyanates. Such polyisocyanates can also contain bothaliphatic and aromatic substituents.

Preferred as the (poly)isocyanate reactant for all the embodiments ofthe invention herein are hexamethylene diisocyanate homopolymerscommercially available, for instance as DESMODUR N-100, DESMODUR N-75and DESMODUR N-3200 from Bayer Corporation, Pittsburgh, Pa.;3-isocyanatomethyl-3,4,4-trimethylcyclohexyl isocyanate available, forinstance as DESMODUR I (Bayer Corporation);bis-(4-isocyanatocylohexyl)methane available, for instance as DESMODUR W(Bayer Corporation) and diisocyanate trimers of formulas:

The diisocyanate trimers (VIIIa-e) are available, for instance asDESMODUR Z4470, DESMODUR IL, DESMODUR N-3300, DESMODUR XP2410, DESMODURN100, respectively, from Bayer Corporation. In one embodiment, G isselected from Formulas (IIIa), (IIIb), (IIIc), (IIId), or (IIIe):

In one embodiment, G is bonded with a monovalent blocking group throughV. Such blocking groups are formed from compounds having oneisocyanate-reactive group. In another embodiment, G-V is bonded with thepolymer backbone through a multifunctional chain extender. Such chainextenders have 2 or more isocyanate-reactive functional groups. Examplesof blocking compounds and chain-extenders include but are not limited towater, substituted sugar alcohol compounds (d) as described above,organic compounds of Formula (IXa)R¹⁵-L  (IXa), ororganic compounds of Formula (IXb)R¹⁴—(OCH₂CH(OR¹⁴)CH₂)_(z)—OR¹⁴  (IXb),or mixtures thereof, wherein R¹⁵ is selected from a C₁ to C₃₀ linear orbranched alkyl optionally comprising at least one unsaturated group, aC₁ to C₂₀ linear or branched fluoroalkyl optionally interrupted by O,CH₂, CH₂CH₂, or SO₂NH, a hydroxy-functional C₁ to C₃₀ linear or branchedalkyl, a hydroxy-functional linear or branched C₁ to C₃₀ polyether, ahydroxy-functional linear or branched polyester having a polyesterpolymer backbone, a hydroxy-functional linear or branchedorganosiloxane, an amine-functional linear or branched organosiloxane, athiol-functional C₁ to C₃₀ linear or branched alkyl, an amine-functionalC₁ to C₃₀ linear or branched alkyl,

or mixtures thereof; L is selected from —N(R²²)H, —OH, —COOH, —SH,—O—(CH₂CH₂O)_(m)(CH(CH₃)CH₂O)_(n)—H, or(C(O)—O—(CH₂CH₂O)_(m)(CH(CH₃)CH₂O)_(n)H; R¹⁶, R¹⁷, and R¹⁸ are eachindependently, —H, —C₁ to C₆ alkyl, or combinations thereof; R²⁰ is adivalent alkyl group of 1 to 20 carbons; R¹⁴ is independently selectedfrom —H; —R²¹; or —C(O)R²¹, provided that at least one R¹⁴ is —H; z isdefined as above; R²² is —H or a monovalent C₁ to C₆ alkyl group; R¹⁸ isdefined as above; and m and n are defined as above. The term “branched”,as used herein, means that the functional chain can be branched at anypoint, for example as a quarternary substituted carbon, and can containany number of branched substitutions. In one embodiment, V is bonded toat least one blocking group selected from a C₁ to C₃₀ linear or branchedalkyl optionally comprising at least one unsaturated group, a linear orbranched C₁ to C₃₀ polyether, a residue X as defined above, or a C₁ toC₂₀ linear or branched fluoroalkyl optionally interrupted by O, CH₂,CH₂CH₂, or SO₂NH.

In one embodiment, L is —O—(CH₂CH₂O)_(m)(CH(CH₃)CH₂O)_(n)—H or—[C(O)]—O—(CH₂CH₂O)_(m)(CH(CH₃)CH₂O)_(n)—H. In this embodiment,—(CH₂CH₂O)— represents oxyethylene groups (EO) and —(CH(CH₃)CH₂O)—represents oxypropylene groups (PO). These polyethers can contain onlyEO groups, only PO groups, or mixtures thereof. These polyethers canalso be present as a tri-block copolymer designated PEG-PPG-PEG(polyethylene glycol-polypropylene glycol-polyethylene glycol).Preferably, the polyethers are the commercially availablemethoxypolyethylene glycols (MPEG's), or mixtures thereof. Alsocommercially available, and suitable for the preparation of thecompositions of the present invention, are butoxypolyoxyalkylenescontaining equal amounts by weight of oxyethylene and oxypropylenegroups (Union Carbide Corp. 50-HB Series UCON Fluids and Lubricants) andhaving an average molecular weight greater than about 1000. In oneaspect, the hydroxy-terminal polyethers of Formula (VIa) have an averagemolecular weight equal to or greater than about 200. In another aspect,the average molecular weight is between 350 and 2000.

In another embodiment, L is —OH, —C(O)OH, —SH, or —NH(R²²); and R¹⁵ isselected from a C₁ to C₃₀ linear or branched alkyl optionally comprisingat least one unsaturated group, a C₁ to C₂₀ linear or branchedfluoroalkyl optionally interrupted by O, CH₂, CH₂CH₂, or SO₂NH, ahydroxy-functional C₁ to C₃₀ linear or branched alkyl, ahydroxy-functional linear or branched C₁ to C₃₀ polyether, ahydroxy-functional linear or branched polyester having a polyesterpolymer backbone, a hydroxy- or amine-functional linear or branchedorganosiloxane, a thiol-functional C₁ to C₃₀ linear or branched alkyl,an amine-functional C₁ to C₃₀ linear or branched alkyl.

Where L is —OH, examples of reagents include but are not limited toalkyl alcohols such as propanol, butanol, or fatty alcohols includingstearyl alcohol (R¹⁵ is a —C₁ to C₃₀ linear or branched alkyl optionallycomprising at least one unsaturated group); alkyl diols or polyols suchas ethanediol, propanediol, butanediol, or hexanediol (R¹⁵ is ahydroxy-functional C₁ to C₃₀ linear or branched alkyl); alkylene glycolethers such as triethylene glycol, tetraethylene glycol, poly(ethyleneglycol) (PEG), poly(propylene glycol) (PPG), poly(tetrahydrofuran), orglycol ethers having mixtures of PEG, PPG, or THF units (R¹⁵ is ahydroxy-functional linear or branched C₁ to C₃₀ polyether); polyesterpolyols (R¹⁵ is a hydroxy-functional linear or branched polyester havinga polyester polymer backbone); silicone prepolymer polyols (R¹⁵ is ahydroxy-functional linear or branched organosiloxane);N,N-dimethylaminoethanol (R¹⁵ is an amine-functional C₁ to C₃₀ linear orbranched alkyl); choline chloride or betaine HCl; or butanone oxime. Thepolyether polyols can contain only EO groups, only PO groups, only THFgroups, or mixtures thereof. These polyethers can also be present as ablock copolymer, such as that designated by PEG-PPG-PEG (polyethyleneglycol-polypropylene glycol-polyethylene glycol). In one aspect, thepolyether glycols have an average molecular weight equal to or greaterthan about 200. In another aspect, the average molecular weight isbetween 350 and 2000. Suitable fluorinated alcohols include but are notlimited to R_(f)CH₂CH₂OH, R_(f)SO₂NHCH₂CH₂OH, R_(f)CH₂CH₂SCH₂CH₂OH,R_(f)CH₂CH₂CF₂CF₂CH₂CH₂OH, R_(f)CH₂CH₂(CF₂CF₂CH₂CH₂)₂OH,R_(f)CH₂CF₂CH₂CH₂OH, R_(f)CH₂CF₂CH₂CF₂CH₂CH₂OH, R_(f)OCF₂CF₂CH₂CH₂OH,R_(f)CH₂OCH₂CH₂OH, R_(f)CHFCH₂CH₂OH, R_(f)CH₂O(CH₂)₆OH,(CF₃)₂CFCH₂CH₂OH, (CF₃)₂CFCH₂CH₂CH₂OH, R_(f)CH₂CH₂SO₂NHCH₂CH₂OH,R_(f)CH₂CH₂SO₂N(CH₃)CH₂CH₂OH, R_(f)CH₂CH₂SO₂N(CH₂CH₃)CH₂CH₂OH,R—(CF(CF₃)CF₂O)_(y)CH₂OH, CF₂═CFOCF₂CF(CF₃)OCF₂CF₂CH₂OH, orR_(f)CH₂OC₂F₄CH₂OCH₂CH₂OH, where R_(f) is a perfluoroalkyl of C₁-C₂₀.

Where L is —COOH, examples include but are not limited to fatty acidssuch as caprylic acid, capric acid, lauric acid, mysteric acid, palmiticacid, stearic acid, arachidic acid, behenic acid, lignoceric acid,palmitoleic acid, lineolic acid, arachidonic acid, oleic acid, or erucicacid (R¹⁵ is a —C₁ to C₃₀ linear or branched alkyl optionally comprisingat least one unsaturated group); hydroxy-containing acids such ashydroxycaprylic acid, hydroxycapric acid, hydroxylauric acid,hydroxymysteric acid, hydroxypalmitic acid, hydroxystearic acid,hydroxyarachidic acid, hydroxybehenic acid, hydroxylignoceric acid,hydroxypalmitoleic acid, hydroxylineolic acid, hydroxyarachidonic acid,hydroxyoleic acid, or hydroxyerucic acid (R¹⁵ is a hydroxy-functional C₁to C₃₀ linear or branched alkyl); and mercaptoalkanoic acids such asmercaptopropionic acid (R¹⁵ is a thiol-functional C₁ to C₃₀ linear orbranched alkyl).

Where L is —SH, specific examples include but are not limited to alkylthiols such as lauryl mercaptan or dodecyl mercaptan (R¹⁵ is a —C₁ toC₃₀ linear or branched alkyl optionally comprising at least oneunsaturated group). Where L is —NH(R²²), specific examples include butare not limited to alkyl amines such as diisopropylamine, propylamine,hexylmine, or laurylamine (R¹⁵ is a C₁ to C₃₀ linear or branched alkyloptionally comprising at least one unsaturated group); alkanolaminessuch as ethanolamine or propanolamine (R¹⁵ is a hydroxy-functional C₁ toC₃₀ linear or branched alkyl); silicone prepolymer polyamines (R¹⁵ is aamine-functional linear or branched organosiloxane); alkyl diamines (R¹⁵is an amine-functional C₁ to C₃₀ linear or branched alkyl); andaminoalkanesulfonic acids such as 2-aminoethanesulfonic acid.

In a further embodiment, the blocking or extender compound comprisesfits Formula (IXb). Such compounds are commonly referred to aspolyglycerols. These polyglycerols can be present where R¹⁴ isindependently a —H; —R²¹; —C(O)R²¹ provided that at least one R¹⁴ is a—H; and wherein R²¹ is independently a linear or branched alkyl grouphaving 5 to 29 carbons optionally comprising at least 1 unsaturatedbond. Specific examples include but are not limited to triglycerolmonostearate, triglycerol distearate, hexaglycerol monostearate,hexaglycerol distearate, decaglyceryl mono(carpylate/caprate),decaglyceryl di(carpylate/caprate), decaglycerol, polyglycerol-3, andC₁₈ diglyceride.

In one embodiment, the polymer comprises more than one type of blockinggroup or chain extender. In addition to compounds of the presentinvention as described herein, these compositions may also compriseadditional compounds that are present from commercially availablesorbitans, polysorbates, alkyl citrates, or pentaethritols. Thesecompounds can be present as a mixture of the various substituted sugaralcohols from fully unsubstituted to fully substituted, and the varioussubstitutions in between, and optionally, the linear or branched alkylgroup having 5 to 29 carbons comprises at least 1 unsaturated bond.

The urethane, urea, or thiourea polymer compound is preferably part ofan aqueous composition, which may further comprise a solvent selectedfrom organic solvents. The aqueous composition is in the form of anaqueous solution, an aqueous emulsion, or an aqueous dispersion.

Aqueous compositions of the urethane, urea, or thiourea polymers can bemade by reacting an isocyanate-reactive ethylenically unsaturatedpolymer with at least one diisocyanate or polyisocyanate. Blockingagents or chain extenders may be added during this step or sequentially.This reaction is typically conducted by charging a reaction vessel withthe diisocyanate or polyisocyanate, the isocyanate-reactiveethylenically unsaturated polymer, and optionally a blocking agent orchain extender. The order of reagent addition is not critical, but ifwater is used, the water should be added after the isocyanates andisocyanate-reactive polymer are reacted.

The specific weight of the reactants charged is based on theirequivalent weights and on the working capacity of the reaction vessel,and is adjusted so that the isocyanate-reactive polymer will be consumedin the first step. A suitable dry organic solvent free ofisocyanate-reactive groups is typically used as a solvent. Ketones arethe preferred solvents, and methylisobutylketone (MIBK) is particularlypreferred for convenience and availability. The charge is agitated, andtemperature adjusted to about 40° C. to 70° C. Typically, a catalystsuch as iron(III) chloride in an organic solvent is then added,typically in an amount of from about 0.01 to about 1.0 weight % based onthe dry weight of the composition, and the temperature is raised toabout 80° C. to 100° C. A co-catalyst, such as sodium carbonate, mayalso be used. If water is to be added, the initial reaction is conductedso that less than 100% of the isocyanate groups are reacted. In thesecond step after holding for several hours, additional solvent, water,and optionally a second compound are added. In one embodiment, themixture is allowed to react for several more hours or until all of theisocyanate has been reacted. Additional water can then be added alongwith surfactants, if desired, to the urethane compounds and stirreduntil thoroughly mixed. Following a homogenization or sonification step,the organic solvent can be removed by evaporation at reduced pressure,and the remaining aqueous solution or dispersion of the compound of thepresent invention can be used as is or subjected to further processing.Preferably, the final compound contains 0% to about 1% of reactiveisocyanate groups. In one embodiment, the molecular weight of the finalurethane, urea, or thiourea polymer is at least 10,000 g/mol.

It will be apparent to one skilled in the art that many changes to anyor all of the above procedures can also be used to optimize the reactionconditions for obtaining maximum yield, productivity, or productquality.

The resulting polymers are useful for providing surface effects to afibrous substrate, including water repellency and optionally stainrelease properties. In one embodiment, the invention is a method oftreating a fibrous substrate comprising applying to the surface of asubstrate a polymer of the invention. The polymer composition above iscontacted with the substrate by any suitable method. Such methodsinclude, but are not limited to, application by exhaustion, foam,flex-nip, nip, pad, kiss-roll, beck, skein, winch, liquid injection,overflow flood, roll, brush, roller, spray, dipping, immersion, and thelike. The composition is also contacted by use of a beck dyeingprocedure, continuous dyeing procedure or thread-line application.

The polymer of the present invention is applied to the substrate assuch, or in combination with other optional textile finishes or surfacetreating agents. Such optional additional components include treatingagents or finishes to achieve additional surface effects, or additivescommonly used with such agents or finishes. Such additional componentscomprise compounds or compositions that provide surface effects such asno iron, easy to iron, shrinkage control, wrinkle free, permanent press,moisture control, softness, strength, anti-slip, anti-static, anti-snag,anti-pill, stain release, soil repellency, soil release, waterrepellency, odor control, antimicrobial, sun protection, cleanabilityand similar effects. Such components may be fluorinated ornon-fluorinated. One or more of such treating agents or finishes areapplied to the substrate before, after, or simultaneously with thecomposition of the present invention. For example, for fibroussubstrates, when synthetic or cotton fabrics are treated, use of awetting agent can be desirable, such as ALKANOL 6112 available from E.I. du Pont de Nemours and Company, Wilmington, Del. When cotton orcotton-blended fabrics are treated, a wrinkle-resistant resin can beused such as PERMAFRESH EFC available from Omnova Solutions, Chester,S.C.

Other additives commonly used with such treating agents or finishes arealso optionally present, such as surfactants, pH adjusters, crosslinkers, wetting agents, wax extenders, and other additives known bythose skilled in the art. Suitable surfactants include anionic,cationic, nonionic, N-oxides and amphoteric surfactants. Examples ofsuch additives include processing aids, foaming agents, lubricants,anti-stains, and the like. The composition is applied at a manufacturingfacility, retailer location, or prior to installation and use, or at aconsumer location.

Optionally, a blocked isocyanate is added with the composition of thepresent invention to further promote durability (i.e., as a blendedcomposition). An example of a suitable blocked isocyanate to use in thepresent invention is PHOBOL XAN available from Huntsman Corp, Salt LakeCity, Utah Other commercially available blocked isocyanates are alsosuitable for use herein. The desirability of adding a blocked isocyanatedepends on the particular application for the copolymer. For most of thepresently envisioned applications, it does not need to be present toachieve satisfactory cross-linking between chains or bonding to thesubstrate. When added as a blended isocyanate, amounts up to about 20%by weight are added.

The optimal treatment for a given substrate depends on (1) thecharacteristics of the compound or composition of the present invention,(2) the characteristics of the surface of the substrate, (3) the amountof compound or composition of the present invention applied to thesurface, (4) the method of application of the compound or composition ofthe present invention onto the surface, and many other factors. Somecompounds or compositions of the present invention work well on manydifferent substrates and are repellent to water. Dispersions preparedfrom compounds of the present invention are generally applied to fibroussubstrates by spraying, dipping, padding, or other well-known methods.After excess liquid has been removed, for example by squeeze rolls, thetreated fibrous substrate is dried and then cured by heating, forexample, to from about 100° C. to about 190° C., for at least 30seconds, typically from about 60 to about 240 seconds. Such curingenhances oil-, water- and soil repellency and durability of therepellency. While these curing conditions are typical, some commercialapparatus may operate outside these ranges because of its specificdesign features.

In another embodiment, the present invention is a fibrous substratetreated by contacting a fibrous substrate with the polymer describedabove. Suitable substrates include fibers, yarns, fabrics, fabricblends, textiles, nonwovens, paper, leather, and carpets. These are madefrom natural or synthetic fibers including cotton, cellulose, wool,silk, rayon, nylon, aramid, acetate, acrylic, jute, sisal, sea grass,coir, polyamide, polyester, polyolefin, polyacrylonitrile,polypropylene, polyaramid, or blends thereof. By “fabric blends” ismeant fabric made of two or more types of fibers. Typically these blendsare a combination of at least one natural fiber and at least onesynthetic fiber, but also can include a blend of two or more naturalfibers or of two or more synthetic fibers. The nonwoven substratesinclude, for example, spunlaced nonwovens, such as SONTARA availablefrom E. I. du Pont de Nemours and Company, Wilmington, Del., andspunbonded-meltblown-spunbonded nonwovens. The treated substrates of thepresent invention have excellent water repellency and optionally stainrelease properties.

The treated substrates of the present invention are useful in a varietyof applications and products such as clothing, protective garments,carpet, upholstery, furnishings, and other uses. The excellent surfaceproperties described above help to maintain surface cleanliness andtherefore can permit longer use.

Test Methods and Materials

All solvents and reagents, unless otherwise indicated, were purchasedfrom Sigma-Aldrich, St. Louis, Mo., and used directly as supplied.Methyl isobutyl ketone (MIBK) and poly(ethylene glycol) methacrylateMW=360 (7-EO methacrylate) are both available from Sigma-Aldrich, St.Louis, Mo.

NUJOL is a mineral oil having a Saybolt viscosity of 360/390 s at 38° C.and a specific gravity of 0.880/0.900 g/cm3 at 15° C., available fromPlough, Inc., Kenilworth, N.J.

Sorbitan tristearate are commercially available from Croda, EastYorkshire, England, or DuPont Nutrition & Health, Copenhagen, Denmark.

2-Methyl-2-propenoic acid, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylester (62-FMA) and 2-propenoic acid,3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl ester (62-FA), and3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoro-1-octanol (6,2-alcohol) arecommercially available from DuPont Chemicals and Fluoroproducts,Wilmington, Del.

N-(isobutoxymethyl)methacrylamide was obtained from Polysciences, Inc.,Warrington, Pa.

DESMODUR N-100 is available from Bayer, Pittsburgh, Pa.

The following test methods and materials were used in the examplesherein.

Test Method 1—Fabric Treatment

The fabrics treated in this study were 100% by weight khaki cotton twillavailable from SDL Atlas Textile Testing Solutions, Rock Hill, S.C.29732 and 100% by weight red polyester fabric available from L. MichaelOY, Finland. The fabric was treated with the aqueous dispersions ofvarious emulsion polymers using a conventional pad bath (dipping)process. The prepared concentrated dispersions were diluted withdeionized water to achieve a pad bath having 60 g/L or 100 g/L of theproduct in the bath. For the treatment of the cotton fabric, a wettingagent, INVADINE PBN and a catalyzed cross-linking agent, KNITTEX 7636(all available from Huntsman, Salt Lake City, Utah) were also includedin the bath at 5 g/L and 30 g/L respectively. The fabric was padded inthe bath, and the excess liquid was removed by squeeze rollers. The wetpickup was around 95% on the cotton substrate. The “wet pick up” is theweight of the bath solution of the emulsion polymer and additivesapplied to the fabric, based on the dry weight of the fabric. The fabricwas cured at approximately 165° C. for 3 minutes and allowed to “rest”after treatment and cure for at least 15 hours.

For the treatment of the polyester fabric, a wetting agent, INVADINE PBN(available from Huntsman, Charlotte, N.C., USA) and 20% acetic acid werealso included in the bath at 5 g/L and 1 g/L respectively. The fabricwas padded in the bath, and the excess liquid removed by squeezerollers. The wet pickup was around 55% on the polyester substrate. The“wet pick up” is the weight of the bath solution of the emulsion polymerand additives applied to the fabric, based on the dry weight of thefabric. The fabric was cured at approximately 160° C. for 2 minutes andallowed to “rest” after treatment and cure for about 15 to about 18hours.

Test Method 2—Water Drop

The water repellency of a treated substrate was measured according tothe DuPont Technical Laboratory Method as outlined in the TEFLON GlobalSpecifications and Quality Control Tests information packet. The testdetermines the resistance of a treated substrate to wetting by aqueousliquids. Drops of water-alcohol mixtures of varying surface tensions areplaced on the fabric and the extent of surface wetting is determinedvisually. The test provides a rough index of aqueous stain resistance.The higher the water repellency rating, the better the resistance thefinished substrate has to staining by water-based substances. Thecomposition of standard test liquids is shown in the following Table 1.Ratings of 0.5 increments are determined by subtracting one half fromthe numbers in Table 1 for borderline passing of the test liquid.

TABLE 1 Standard Test Liquids Water Repellency Composition Vol. %,Composition, Vol. % Rating Number Isopropyl Alcohol Distilled Water 1 298 2 5 95 3 10 90 4 20 80 5 30 70 6 40 60 7 50 50 8 60 40 9 70 30 10 8020 11 90 10 12 100 0Test Method 3—Oil Repellency

The treated fabric samples were tested for oil repellency by amodification of AATCC standard Test Method No. 118, conducted asfollows: A fabric sample, treated with an aqueous dispersion of polymer,was conditioned for a minimum of 15 hours at 23° C.+65% relativehumidity prior to testing. A series of organic liquids, identified belowin Table 2, were then applied drop wise to the fabric samples. Beginningwith the lowest numbered test liquid (Repellency Rating No. 1), one drop(approximately 5 mm in diameter or 0.05 mL volume) was placed on each ofthree locations at least 5 mm apart. The drops were observed for 30seconds. If, at the end of this period, two of the three drops werestill spherical in shape with no wicking around the drops, three dropsof the next highest numbered liquid were placed on adjacent sites andsimilarly observed for 30 seconds. The procedure was continued until oneof the test liquids resulted in two of the three drops failing to remainspherical to hemispherical, or wetting or wicking occurred.

The oil repellency rating of the fabric was the highest numbered testliquid for which two of the three drops remained spherical tohemispherical, with no wicking for 30 seconds. Ratings of 0.5 incrementswere determined by subtracting one-half from the number in Table 2 forborderline passing of the next liquid. Higher ratings indicate greaterrepellency. The composition of oil repellency test liquids is shown inthe Table 2.

TABLE 2 Oil Repellency Test Liquids Oil Repellency Rating Test Solution1 NUJOL Purified Mineral Oil 2 65/35 NUJOL/n-hexadecane by volume at 21°C. 3 n-hexadecane 4 n-tetradecane 5 n-dodecane 6 n-decaneTest Method 4—Spray Test

The dynamic water repellency of treated substrates was measuredaccording to the American Association of Textile Chemists and Colorists(AATCC) TM-22. Samples are visually scored by reference to publishedstandards, with a rating of 100 denoting no water penetration or surfaceadhesion. A rating of 90 denotes slight random sticking or wettingwithout penetration; lower values indicate progressively greater wettingand penetration. Test Method 2, the dynamic water repellency test, is ademanding and realistic test of water repellency.

Test Method 5—Stain Release

This test measures the ability of a fabric to release oily stains duringhome laundering.

Treated textiles are placed on a flat surface. Using an eyedropper, 5drops of MAZOLA Corn Oil or mineral oil (0.2 mL) were placed onto thefabric to form 1 drop of oil. A weight (5 lb, 2.27 kg) is placed on topof the oil drop with a piece of glassine paper separating the oil drop.The weight was left in place for 60 seconds. After 60 seconds, theweight and glassine paper are removed. The textiles samples were thenwashed using a automatic washer high for 12 minutes with AATCC 1993Standard Reference Detergent WOB12 or granular detergent (100 g). Thetextiles were then dried on high for 45-50 minutes. The textiles werethen evaluated for residual stain of 1 to 5, 1 having the largestresidual stain remaining and 5 being no stain residual was visible. Inthe examples below, stain release ratings of corn oil are designated bythe term “Corn Oil”, and stain release ratings of mineral oil aredesignated by the term “Mineral Oil”.

Examples of the compounds and compositions of the instant invention canbe made from various reactive ethylenically unsaturated monomers andvarious substituted sugar alcohols, or mixtures thereof. The presentinvention is not to be limited by the examples below.

Comparative Example A

Untreated fabric samples were tested according to the test methodsabove. Both cotton and polyester fabrics had a water drop rating of 0,an oil drop rating of 0, and a spray rating of 0.

Preparation of a Sorbitan Tristearate Methacrylate Monomer (M1)

CH₂═C(CH₃)—C(O)-STS, where STS is the residue of sorbitan tristearate

A dry 1-L round bottom four neck flask was assembled with athermocouple, mechanical stirrer, a nitrogen inlet, condenser, and gasoutlet. The flask was charged with sorbitan tristearate (100 g, OH value76, 162.57 mmol), dichloromethane (300 g), and triethylamine (17.82 g,176.11 mmol). Methacryloyl chloride (15.79 mL, 162.57 mmol) was slowlyadded to the solution via syringe. The flask was insulated with foil.The reaction mixture was stirred under nitrogen at room temperature for48 hours, at which point 200 mL of ether was added. Triethyl ammoniumchloride was removed by filtration. Organic layers were washed with 5 wt% acetic acid solution (250 mL), the aqueous layer was extracted withdichloromethane, and the organic layers were washed with saturatedNaHCO₃ solution. The organic layers were dried with MgSO₄ and filtered.0.01 g of p-methoxyphenol polymerization inhibitor was added, andorganic solvent was removed via rotary evaporation without heating. Theproduct was a light yellow solid at room temperature.

Preparation of a Sorbitan Tristearate Urethane Methacrylate (M2)

CH₂═C(CH₃)—C(O)OCH₂CH₂NHC(O)-STS, where STS is the residue of sorbitantristearate

A dry 4-neck 500 mL round bottom flask was assembled with athermocouple, mechanical stirrer, nitrogen inlet, condenser, and gasoutlet. The flask was charged with 2-isocyanatoethyl methacrylate (25.0g, 161.13 mmol), MIBK (141.44 g), and a solution of 0.50 weight % FeCl₃in MIBK (2.5 g). The mixture was heated to 60° C., and sorbitantristearate (118.94 g, OH value 76) was added to the flask. Thetemperature was then raised to 80° C. and stirred overnight. After 24hours, 1,8-diazabicycloundec-7-ene (0.05 g) was added, and the reactionmixture was stirred for another 24 hours at 80° C. When the solutiontested negative for isocyanates, it was filtered through a milk filterand collected.

Preparation of a Sorbitan Tristearate Urethane Styrene Monomer (M3)

CH₂═CH—(C₆H₄)—C(CH₃)₂—NHC(O)-STS, where STS is the residue of sorbitantristearate

A dry 4-neck 500 mL round bottom flask was assembled with athermocouple, mechanical stirrer, nitrogen inlet, condenser, and gasoutlet. The flask was charged with 3-isopropenyl-α,α-dimethylbenzylisocyanate (36.0 g, 178.8 mmol), MIBK (168 g), a solution of 0.50 weight% FeCl₃ in MIBK (6.0 g), and 1,8-diazabicycloundec-7-ene (0.1 g). Themixture was heated to 60° C. Sorbitan tristearate (132.04 g, 178.8 mmol)was added to the flask. The temperature was then raised to 80° C. andstirred overnight. When the solution tested negative for isocyanates, itwas cooled to 45° C., filtered through a milk filter, and collected.

Preparation of Methacrylic Polymers 1-4 (P1-P4)

Stock solution of 7-EO methacrylate, N-iso-butoxymethylmethacrylamide,hydroxyethyl methacrylate, and dodecyl mercaptan was prepared at 50% byweight in MIBK according to the amounts in Table 3. Additional monomersand MIBK were combined with stock solution and initiator in a 30-mLvial. The vial was capped and a nitrogen line was connected. Mostreactions run at 25-40% solids in MIBK. The reaction was heated to 80°C. overnight. When vinylidene chloride was present, the reaction mixturewas instead heated to 50° C. and then temperature was slowly increasedto 80° C. (10° C. every 15 minutes) and stirred overnight.

TABLE 3 Reagents of Polymers P1-P4 Example P1 P2 P3 P4 Reagents (g) M12.38 10.94  2.37 10.92  6,2-FMA 4.00 — 4.00 — 7-EO methacrylate 0.080.08 0.08 0.08 Stearyl methacrylate 1.00 — 1.03 — N-iso-butoxymethyl0.11 0.11 0.11 0.11 methacrylamide Hydroxyethyl methacrylate 0.09 0.090.09 0.09 Dodecyl mercaptan 0.03 0.03 0.03 0.03 Vinylidene chloride — —0.72 0.67 VAZO 67 0.13 0.13 0.15 0.14Preparation of Urethane Methacrylic Polymers 5-8 (P5-P8)

The synthesis of P1 was repeated using the reagents of Table 4.

TABLE 4 Reagents of Polymers P5-P8 Example P5 P6 P7 P8 Reagents (g) M22.64 11.60  2.79 12.12  6,2-FMA 4.00 — 4.00 — 7-EO methacrylate 0.080.08 0.08 0.08 Stearyl methacrylate 1.01 — 1.03 — N-iso-butoxymethyl0.11 0.11 0.11 0.11 methacrylamide Hydroxyethyl methacrylate 0.09 0.090.09 0.09 Dodecyl mercaptan 0.03 0.03 0.03 0.03 Vinylidene chloride 0.670.69 VAZO 67 0.13 0.13 0.15 0.14Preparation of Polymers 9-12 (P9-P12)

The synthesis of P1 was repeated using the reagents of Table 5.

TABLE 5 Reagents of Polymers P9-P12 Example P9 P10 P11 P12 Reagents (g)M3 2.77 12.74  2.77 12.73  6,2-FMA 4.01 — 4.01 — 7-EO methacrylate 0.080.08 0.08 0.08 Stearyl methacrylate 1.02 — 1.00 — N-iso-butoxymethyl0.11 0.11 0.11 0.11 methacrylamide Hydroxyethyl methacrylate 0.09 0.090.09 0.09 Dodecyl mercaptan 0.03 0.03 0.03 0.03 Vinylidene chloride 0.660.67 VAZO 67 0.13 0.13 0.14 0.14Preparation of Polymers 13-18 (P13-P18)

The monomers and initiator were added into a 30 mL vial according to theamounts listed in Table 6. The vial was capped and a nitrogen line wasconnected. The reaction mixture was heated to 80° C. and stirredovernight.

TABLE 6 Reagents of Polymers P13-P18 Example P13 P14 P15 P16 P17 P18Reagent Amounts (g) M1 2.59 12.34 — — — — M2 — — 2.87 9.57 — — M3 — — —— 3.02 10.06  6,2-FMA 4.64 — 4.64 — 4.64 — Hydroxyethyl 1.1  1.1 1.1 0.77 1.1  0.77 methacrylate Stearyl 1.04 — 1.04 — 1.04 — methacrylateVAZO 67 0.08  0.08 0.08 0.08 0.08 0.08

Examples 1-4

Amounts of reagents are listed in Table 7. In a small vial, sorbitantristearate, sodium carbonate, isocyanate-reactive polymer (0.00045 molOH) and excess MIBK were mixed in a 30-mL vial and heated to 55° C.under nitrogen atmosphere. Once the temperature stabilized, DESMODURN100 was added and the temperature was increased to 80° C. Aftertemperature reached 80° C., FeCl₃ catalyst was added (0.02-0.04 g, 0.5weight % solution in MIBK) and the reaction was heated at 95° C. for 4hours. After 4 hours, n-butanol (0.02 g) was added, and the temperaturewas reduced to 90° C. overnight. If the reaction tested positive foractive isocyanates, additional catalyst and water were added to quenchthe reaction. When the reaction tested negative for active isocyanates,the reaction was diluted to 10% solids in MIBK, applied to fabric, andtested according to the above test methods.

TABLE 7 Reagents and Performance of Examples 1-4 Example 1 2 3 4Hydroxy-functional Polymer Polymer Used P1 P2 P3 P4 Amount Used (g) 4.675.56 4.19 7.01 Additional Reagents Sorbitan tristearate (g) 1.12 0.830.84 0.84 Sodium Carbonate (g) 0.01 0.02 0.02 0.01 DESMODUR N100 (g)0.41 0.31 0.28 0.29 N-butanol 0.02 0.02 0.03 0.03 Cotton PerformanceWater Drop 10 4 11 5 Oil Drop 5 0 5 0 Spray 90 90 85 85 PolyesterPerformance Water Drop 7 4 8 3 Oil Drop 4 0 4 0 Spray 95 90 85 95

Examples 5-8

Example 1 was repeated, using the reagents in Table 8.

TABLE 8 Reagents and Performance of Examples 5-8 Example 5 6 7 8Hydroxy-functional Polymer Polymer Used P5 P6 P7 P8 Amount Used (g) 3.826.08 4.33 6.13 Additional Reagents Sorbitan tristearate (g) 0.84 0.830.83 0.84 Sodium Carbonate (g) 0.01 0.01 0.02 0.01 DESMODUR N100 (g)0.28 0.31 0.30 0.27 N-butanol 0.02 0.02 0.02 0.03 Cotton PerformanceWater Drop 10 4 10 4 Oil Drop 5 0 5 0 Spray 90 95 80 100 PolyesterPerformance Water Drop 8 4 8 3 Oil Drop 4 0 4 0 Spray 90 95 90 100

Examples 9-12

Example 1 was repeated, using the reagents in Table 9.

TABLE 9 Reagents and Performance of Examples 9-12 Example 9 10 11 12Hydroxy-functional Polymer Polymer Used P9 P10 P11 P12 Amount Used (g)4.04 8.41 4.33 6.86 Additional Reagents Sorbitan tristearate (g) 0.830.83 0.84 0.83 Sodium Carbonate (g) 0.01 0.02 0.01 0.01 DESMODUR N100(g) 0.27 0.43 0.31 0.29 N-butanol 0.02 0.02 0.02 0.03 Cotton PerformanceWater Drop 10 4 10 4 Oil Drop 5 0 5 0 Spray 85 85 80 80 PolyesterPerformance Water Drop 8 3 8 4 Oil Drop 4 0 4 0 Spray 95 85 90 80

Examples 13-15

Example 1 was repeated, using the reagents in Table 10.

TABLE 10 Reagents and Performance of Examples 13-15 Example 13 14 15Hydroxy-functional Polymer Polymer Used P13 P14 P14 Amount Used (g) 1.1711.00 1.73 Additional Reagents Sorbitan tristearate (g) 1.66 0.84 1.66Sodium Carbonate (g) 0.02 0.01 0.02 DESMODUR N100 (g) 0.60 0.31 0.60N-butanol 0.04 0.04 0.05 Cotton Performance Water Drop 8 4 4 Oil Drop 40 0 Spray 75 90 100 Polyester Performance Water Drop 5 3 3 Oil Drop 3 00 Spray 80 95 90

Examples 16-19

Example 1 was repeated, using the reagents in Table 11.

TABLE 11 Reagents and Performance of Examples 16-19 Example 16 17 18 19Hydroxy-functional Polymer Polymer Used P15 P15 P16 P16 Amount Used (g)1.36 6.65 1.89 5.34 Additional Reagents Sorbitan tristearate (g) 1.660.83 1.67 0.55 Sodium Carbonate (g) 0.02 0.01 0.02 0.01 DESMODUR N100(g) 0.60 0.29 0.59 0.22 N-butanol 0.05 0.03 0.05 0.01 Cotton PerformanceWater Drop 8 9 4 4 Oil Drop 4 4 0 2 Spray 80 80 90 80 PolyesterPerformance Water Drop 5 7 3 3 Oil Drop 3 3 0 0 Spray 80 80 100 95

Examples 20-23

Example 1 was repeated, using the reagents in Table 12.

TABLE 12 Reagents and Performance of Examples 20-23 Example 20 21 22 23Hydroxy-functional Polymer Polymer Used P17 P17 P18 P18 Amount Used (g)1.20 4.83 2.13 11.80 Additional Reagents Sorbitan tristearate (g) 1.660.84 1.81 1.83 Sodium Carbonate (g) 0.02 0.02 0.03 0.01 DESMODUR N100(g) 0.60 0.30 0.66 0.29 N-butanol 0.04 0.02 0.07 0.02 Cotton PerformanceWater Drop 8 9 3 4 Oil Drop 3 4 0 0 Spray 80 75 75 80 PolyesterPerformance Water Drop 5 7 3 3 Oil Drop 2 3 0 0 Spray 80 85 80 90

Examples 24-28

Amounts of reagents used are shown in Table 12. Into a small vial, N100,sodium carbonate, 6,2 alcohol, and isocyanate-reactive polymer (0.0003mol of OH) were charged and heated to 35° C. The temperature wasgradually increased to 60° C. at a rate of 10° C./10 min. At 60° C.,FeCl₃ catalyst (0.02-0.04 g, 0.5 weight % solution in MIBK) was added,and the reaction was slowly heated to 95° C. at a rate of 5° C./10 min.After 4 hours at 95° C., water was added. The reaction was held at 95°C. overnight. If reaction tested positive for active isocyanates, ˜0.02g of sodium carbonate and extra catalyst were added. Once the reactiontested negative for active isocyanates, the reaction was diluted to 10%solids in MIBK, applied to fabric, and tested according to the abovetest methods.

TABLE 13 Reagents and Performance of Examples 24-28 Example 24 25 26 2728 Hydroxy-functional Polymer Polymer Used P1 P2 P3 P4 P14 Amount Used(g) 3.07 4.46 3.41 4.51 1.49 Additional Reagents 6,2-alcohol (g) 0.140.17 0.13 0.29 0.25 Sodium Carbonate (g) 0.01 0.01 0.03 0.04 0.02DESMODUR N100 (g) 0.29 0.30 0.30 0.30 0.60 Water (g) 0.03 0.04 0.04 0.030.25 Cotton Performance Water Drop 11 4 11 3 4 Oil Drop 5 0 6 2 4 Spray85 80 80 70 70 Polyester Performance Water Drop 8 3 7 3 3 Oil Drop 4 0 41 4 Spray 90 70 95 70 60

Examples 29-34

Example 24 was repeated, using the reagents in Table 14.

TABLE 14 Reagents and Performance of Examples 29-34 Example 29 30 31 3233 3 Hydroxy-functional Polymer Polymer Used P5 P6 P7 P8 P15 P16 AmountUsed (g) 3.10 5.20 3.46 4.96 1.04 1.64 Additional Reagents 6,2-alcohol(g) 0.14 0.15 0.15 0.12 0.26 0.24 Sodium Carbonate (g) 0.01 0.01 0.040.02 0.03 0.02 DESMODUR N100 (g) 0.30 0.30 0.30 0.31 0.60 0.60 Water (g)0.04 0.03 0.04 — — — Cotton Performance Water Drop 11 4 11 4 8 5 OilDrop 3 0 5 0 5 2 Spray 70 80 85 85 80 60 Polyester Performance WaterDrop 7 4 7 3 5 2 Oil Drop 4 2 4 0 3 1 Spray 90 80 80 100 80 60

Examples 35-40

Example 24 was repeated, using the reagents in Table 15.

TABLE 15 Reagents and Performance of Examples 35-40 Example 35 36 37 3839 40 Hydroxy-functional Polymer Polymer Used P9 P10 P11 P12 P17 P18Amount Used (g) 3.32 3.84 3.62 5.18 1.05 1.61 Additional Reagents6,2-alcohol (g) 0.16 0.14 0.13 0.16 0.27 0.24 Sodium Carbonate 0.01 0.010.03 0.02 0.02 0.02 (g) DESMODUR N100 0.30 0.35 0.30 0.30 0.60 0.60 (g)Water (g) 0.04 0.04 0.03 — — — Cotton Performance Water Drop 10 3 9 3 46 Oil Drop 3 1 5 0 2 4 Spray 85 70 80 70 90 60 Polyester PerformanceWater Drop 8 4 7 3 4 3 Oil Drop 4 2 4 1 4 3 Spray 85 70 80 70 70 60

Examples 41-46

Amounts of reagents used are shown in Table 16. In a small vial,DESMODUR N100, FeCl₃ catalyst (0.02-0.04 g, 0.5 weight % solution inMIBK), and extra MIBK (0.65 g) were heated to 60° C. MPEG 750 and sodiumcarbonate were added next and the temperature was increased to 95° C.After holding the reaction for 1 hour at 95° C., isocyanate-reactivepolymer (0.00045 mol OH) was added. The reaction mixture was stirred andheated at 90° C. overnight. If reaction tested positive for activeisocyanates, ˜0.03 g of DI water and extra catalyst were added. Once thereaction testing negative for active isocyanates, the reaction wasdiluted to 10% solids in MIBK, applied to fabric, and tested accordingto the above test methods.

TABLE 16 Reagents and Performance of Examples 41-46 Example 41 42 43 4445 46 Hydroxy-functional Polymer Polymer Used P1 P2 P3 P4 P13 P14 AmountUsed (g) 3.91 5.62 4.20 5.58 1.11 1.20 Additional Reagents MPEG 750 (g)0.71 0.69 0.70 0.74 1.38 1.38 Sodium Carbonate 0.01 0.01 0.01 0.01 0.020.02 (g) DESMODUR N100 0.24 0.25 0.25 0.25 0.50 0.50 (g) Water (g) 0.050.04 — — — — Cotton Performance Water Drop 10 4 8 4 6 3 Oil Drop 5 0 5 04 0 Spray 75 70 70 70 70 60 Corn Oil 3 1 1 1 3 2 Mineral Oil 2 1 1 1 1 2

Examples 47-52

Example 41 was repeated, using the reagents in Table 17.

TABLE 17 Reagents and Performance of Examples 47-52 Example 47 48 49 5051 52 Hydroxy-functional Polymer Polymer Used P5 P6 P7 P8 P15 P16 AmountUsed (g) 3.95 7.31 4.32 6.12 1.36 1.89 Additional Reagents MPEG 750 (g)0.71 0.70 0.70 0.69 1.38 1.38 Sodium Carbonate 0.01 0.01 0.01 0.01 0.020.02 (g) DESMODUR N100 0.24 0.25 0.25 0.25 0.50 0.50 (g) Water (g) — —0.06 — — — Cotton Performance Water Drop 7 4 6 3 6 3 Oil Drop 5 0 5 0 50 Spray 80 70 70 80 70 60 Corn Oil 2 1 2 1 3 3 Mineral Oil 2 1 1 1 2 3

Examples 53-58

Example 41 was repeated, using the reagents in Table 18.

TABLE 18 Reagents and Performance of Examples 53-58 Example 53 54 55 5657 58 Hydroxy-functional Polymer Polymer Used P9 P10 P11 P12 P17 P18Amount Used (g) 4.00 6.46 4.39 6.68 1.06 1.98 Additional Reagents MPEG750 (g) 0.71 0.70 0.70 0.69 1.38 1.38 Sodium Carbonate 0.01 0.01 0.010.01 0.02 0.02 (g) DESMODUR N100 0.24 0.25 0.25 0.25 0.50 0.50 (g) Water(g) — 0.04 0.09 — — — Cotton Performance Water Drop 10 4 8 3 7 3 OilDrop 5 0 6 0 5 0 Spray 70 75 80 70 70 60 Corn Oil 2 3 1 1 3 3 MineralOil 2 2 1 1 2 3

The compounds, compositions, method, and substrates of the presentinvention are useful to provide excellent water repellency andoptionally stain release to treated substrates. The surface propertiesare obtained using a non-fluorinated or partially fluorinated organicpolymer as defined above. The use of non-fluorinated or partiallyfluorinated organic polymers have been found to provide superior waterrepellency and durable water repellency compared to traditionalnon-fluorinated water repellents and are comparable to commerciallyavailable fluorinated water repellents.

What is claimed is:
 1. A method of preparing a polymer compoundcomprising (i) reacting (a) at least one compound selected from Formula(IV)

with (b) at least one compound selected from Formula (V)

(ii) optionally reacting at least one additional ethylenicallyunsaturated monomer; (iii) subsequently reacting the product of step (i)or (ii) with at least one diisocyanate or polyisocyanate; and (iv)optionally reacting at least one isocyanate-reactive compound duringstep (iii) or following step (iii); wherein R³ is selected from H or aC₁ to C₄ alkyl group; Q is C(O)O, C(O)NH, or a direct bond; D is a C₁ toC₆ linear or branched alkylene, an arylene group, or(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m), J is H, OH, N(R⁵)₂, C(O)OH, or SH;provided that J is H only when D is (CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m); R⁵is H or a C₁ to C₆ alkyl; Y is selected from O, a substituted arylenegroup, or an unsubstituted arylene group; A is a linear or branched C₁to C₁₀ alkylene group; w is 0 or 1; v is 0 or 1; y is 0 or 1; providedthat w+y is at least 1; if w is 0 then Y is a substituted orunsubstituted arylene group; and if Y is O then v is 1; X is the residueof a cyclic or acyclic sugar alcohol which is substituted with at leastone —R¹, —C(O)R¹, —(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹, or mixtures thereof; where thecyclic or acyclic sugar alcohol is selected from a saccharide, reducedsugar, aminosaccharide, aldonic acid, or aldonic acid lactone; whereineach n is independently 0 to 20; each m is independently 0 to 20; m+n isgreater than 0; each R¹ is independently a linear or branched alkylgroup having 5 to 29 carbons optionally comprising at least 1unsaturated bond; and each R² is independently H, a linear or branchedalkyl group having 6 to 30 carbons optionally comprising at least 1unsaturated bond, or mixtures thereof.
 2. The method of claim 1, where Xis selected from Formulas (IIa), (IIb), or (IIc):

wherein each R is independently a direct bond to C═O of Formula I, H,—R¹, —C(O)R¹, —(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R², or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹; n and m are defined as above; m+nis greater than 0; r is 1 to 3; a is 0 or 1; p is independently chosenfrom 0 to 2; provided that a is 0 when r is 3; each R¹ and R² aredefined as above; provided when X is Formula (IIa), then one R is adirect bond to C═O of Formula 1; and at least one R is a —R¹, —C(O)R¹,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R², or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹; each R⁴ is independently a directbond to C═O of Formula I, —H, a linear or branched alkyl group having 6to 30 carbons optionally comprising at least 1 unsaturated bond orcombinations thereof, —(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R², or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹; provided when X is Formula (IIb),then one R or R⁴ is a direct bond to C═O of Formula 1; and at least oneR or R⁴ is a linear or branched alkyl group optionally comprising atleast 1 unsaturated bond or combinations thereof,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R², or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹; and each R¹⁹ is a direct bond toC═O of Formula I, —H, —C(O)R¹, or —CH₂C[CH₂OR]₃, provided when X isFormula (IIc), then one R¹⁹ or R is a direct bond to C═O of Formula I;and at least one R¹⁹ or R is —C(O)R¹, —(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²,or —(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹.
 3. The method of claim 1 whereat least one additional ethylenically unsaturated monomer is used,having a functional group selected from a linear or branchedhydrocarbon, linear or branched fluorocarbon, ether, anhydride,oxyalkylene, ester, formate, carbamate, urea, amide, sulfonate, sulfonicacid, sulfonamide, halide, saturated or unsaturated cyclic hydrocarbon,morpholine, pyrrolidine, piperidine, or mixtures thereof.
 4. The methodof claim 3, wherein the additional ethylenically unsaturated monomer isselected from linear or branched alkyl (meth)acrylates, linear orbranched fluoroalkyl (meth)acrylates optionally interrupted by O, CH₂,CH₂CH₂, or SO₂NH, alkoxylated (meth)acrylates, (meth)acylic acid, vinylor vinylidene chloride, glycidyl (meth)acrylate, vinyl acetate,hydroxyalkylene (meth)acrylate, urethane or urea (meth)acrylates,(meth)acrylamides including N-methyloyl (meth)acrylamide, alkoxyalkyl(meth)acrylamide, styrene, alpha-methylstyrene, chloromethyl-substitutedstyrene, ethylenediol di(meth)acrylate, 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), and maleic anhydride.
 5. A method of treating afibrous substrate comprising applying to the surface of a substrate apolymer made by the method of claim
 1. 6. The method of claim 5 whereinthe applying step is performed by exhaustion, foam, flex-nip, nip, pad,kiss-roll, beck, skein, winch, liquid injection, overflow flood, roll,brush, roller, spray, dipping or immersion.
 7. The method of claim 2,wherein X is selected from Formula (IIa) to be Formula (IIa′):

wherein R is further limited to independently a direct bond to C═O, —H,—R¹, or —C(O)R¹.
 8. The method of claim 2, wherein X is selected fromFormula (IIa) to be Formula (IIa′):

wherein R is further limited to independently a direct bond to C═O, —H,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R², or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹.
 9. The method of claim 1,comprising the step of reacting at least one isocyanate-reactivecompound following step (iii), where the isocyanate-reactive compound iswater.